Deposition of thin films on a substrate surface is an important process in a variety of industries including semiconductor processing, diffusion barrier coatings and dielectrics for magnetic read/write heads. In the semiconductor industry, in particular, miniaturization requires atomic level control of thin film deposition to produce conformal coatings on high aspect structures. One method for deposition of thin films with control and conformal deposition is atomic layer deposition (ALD), which employs sequential, surface reactions to form layers of precise thickness. Most ALD processes are based on binary reaction sequences which deposit a binary compound film. Because the surface reactions are sequential, the two gas phase reactants are not in contact, and possible gas phase reactions that may form and deposit particles are limited.
ALD has been used to deposit metals and metal compounds on substrate surfaces. Al2O3 deposition is an example of a typical ALD process illustrating the sequential and self-limiting reactions characteristic of ALD. Al2O3 ALD conventionally uses trimethylaluminum (TMA, often referred to as reaction “A” or the “A” precursor) and H2O (often referred to as the “B” reaction or the “B” precursor). In step A of the binary reaction, hydroxyl surface species react with vapor phase TMA to produce surface-bound AlOAl(CH3)2 and CH4 in the gas phase. This reaction is self-limited by the number of reactive sites on the surface. In step B of the binary reaction, AlCH3 of the surface-bound compound reacts with vapor phase H2O to produce AlOH bound to the surface and CH4 in the gas phase. This reaction is self-limited by the finite number of available reactive sites on surface-bound AlOAl(CH3)2. Subsequent cycles of A and B, purging gas phase reaction products and unreacted vapor phase precursors between reactions and between reaction cycles, produces Al2O3 growth in an essentially linear fashion to obtain the desired film thickness. Because of the usefulness of ALD processes, there is an ongoing need for new ALD chemistries.
Silicon nitride (SiN) is a commonly used dielectric throughout the semiconductor industry. One method of SiN deposition utilizes a halosilane silicon precursor and ammonia co-reactant. A commonly used halosilane is monochlorosilane. The driving force for N—H Cl—Si condensation is very high, leading to HCl formation. However, in the presence of gas phase NH3, NH3 and HCl react to yield NH4Cl(s) (ammonium chloride), which results in particle formation. Moreover, this reaction is in equilibrium at 1 ATM at 330° C. Ammonium chloride has a relatively low vapor pressure and can clog up chamber exhausts. Thus, there is a need for new ALD chemistries which produce byproducts having a higher vapor pressure.
Additionally, there is an increasing need for dielectrics with lower dielectric constant (k) values and with lower etch rates. Thus, there is a need for ALD chemistries of improved dielectrics.
Additionally, a common problem with Si(C)N deposition pertains to ammonium chloride management in the chamber.